Method and apparatus for filling a gap

ABSTRACT

A method and apparatus for filling one or more gaps created during manufacturing of a feature on a substrate by: providing a bottom area of a surface of the one or more gaps with a first reactant; providing a second reactant to the substrate; and, allowing the first reactant to initiate reaction of the second reactant in the bottom area of the surface in a stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactants leaving a top area of the surface of the one or more gaps which was not provided with the first reactant initially substantially empty.

FIELD

The present invention generally relates to methods and apparatus for manufacturing electronic devices.

More particularly, the invention relates to a method and apparatus for filling one or more gaps created during manufacturing of a feature on a substrate for manufacturing electronic devices by a deposition method comprising;

providing a surface of the one or more gaps with a first reactant;

providing a second reactant to the substrate; and,

allowing the first reactant to initiate reaction of the second reactant.

BACKGROUND

During manufacturing of an integrated circuit on a substrate gaps e.g. trenches can be created on the substrate. Refilling the trenches can take a variety of forms depending upon the specific application.

The basic trench filling process may be subjected to drawbacks, including void formation in the trench during refill. Voids may be formed when the refilling material forms a constriction near the top of the trench before it is completely filled. Such voids may compromise device isolation of the devices on the integrated circuit (IC) as well as the overall structural integrity of the IC. Unfortunately, preventing void formation during trench fill may often place size constraints on the trenches, which may limit device packing density of the device.

If the trenches are filled for device isolation a key parameter in measuring the effectiveness of device isolation may be the field threshold voltage, that is, the voltage necessary to create a parasitic current linking adjacent isolated devices. The field threshold voltage may be influenced by a number of physical and material properties, such as trench width, dielectric constant of the trench filling material, substrate doping, field implant dose and substrate bias.

Void formation may be mitigated by decreasing trench depth and/or tapering trench sidewalls so that the openings may be wider at the top than at the bottom. A trade off in decreasing the trench depth may be reducing the effectiveness of the device isolation, while the larger top openings of trenches with tapering sidewalls may use up additional integrated circuit real estate.

SUMMARY

It is an objective, for example, to provide an improved or at least alternative gap filling method.

Accordingly, there is provided a method for filling one or more gaps created during manufacturing of a feature on a substrate by a deposition method comprising;

providing a bottom area of a surface of the one or more gaps with a first reactant;

providing a second reactant to the surface; and,

allowing the first reactant to initiate reaction of the second reactant in the bottom area of the surface in a stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactant leaving a top area of the surface of the one or more gaps which was not provided with the first reactant initially substantially empty.

By having the first reactant initiating reaction of the second reactant in the bottom area of the surface in a stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactants leaving a top area of the surface of the one or more gaps which was not provided with the first reactant initially substantially empty the gap may be filled bottom up pretty quickly without the opening of gap getting constricted.

According to a further embodiment there is provided a semiconductor processing apparatus to provide an improved or at least alternative gap filling method. The apparatus comprising:

one or more reaction chambers for accommodating a substrate provided with gaps created during manufacturing of a feature on the substrate;

a first source for a first reactant in gas communication via a first valve with one of the reaction chambers; and,

a second source for a second reactant in gas communication via a second valve with one of the reaction chambers; wherein the apparatus comprises:

a plasma gas source for a plasma gas in gas communication via a plasma gas valve with one of the reaction chambers;

a radio frequency power source constructed and arranged to create a plasma of the plasma gas;

a heater constructed and arranged to heat the substrate in one of the reaction chambers and,

a controller operably connected to the first, second and plasma gas valve, the radio frequency power source and the heater and configured and programmed to control:

a timing and an amount of the first, the plasma gas, and the radio frequency source to use the first source, the plasma gas source and the radiofrequency power source to provide the first reactant substantially in a bottom area of the surface of the gap; and,

a timing and an amount of the second reactant and the heater to deposit at an alleviated temperature in a stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactants causing a reaction in the gap leaving a top area of the surface of the one or more gaps which was not provided with the first reactant initially substantially empty.

For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention.

Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

All of these embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures, the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the drawings of certain embodiments, which are intended to illustrate and not to limit the invention.

FIG. 1A is a schematic representation of a PEALD (plasma-enhanced atomic layer deposition) apparatus for filling a gap usable in an embodiment of the present invention.

FIG. 1B illustrates a schematic representation of a precursor supply system using a flow-pass system (FPS) usable in an embodiment of the present invention.

FIG. 2 is a flowchart of a method for filling a gap in accordance with a first embodiment.

FIG. 3 is a flowchart of a first method for providing a bottom area of a surface of the one or more gaps with a first reactant for use with the method of FIG. 2.

FIG. 4 is a flowchart of a second method for providing a bottom area of a surface of the one or more gaps with a first reactant for use with the method of FIG. 2.

FIG. 5 is a flowchart of a third method for providing a bottom area of a surface of the one or more gaps with a first reactant for use with the method of FIG. 2.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

FIG. 2 is a flowchart of a method in accordance with at least one embodiment of the invention in which one or more gaps created during manufacturing of a feature on a substrate may be filled by a deposition method 100. The gaps may be less than 40 or even 20 nm wide. The gaps may be more than 40, 100, 200 or even 400 nm deep.

The deposition method may comprise in a first step 110 providing a bottom area of a surface of the one or more gaps with a first reactant. The bottom area of the surface of the one or more gaps may be defined as the lower 75%, 50%, 25% or even 10% of the total height of the gap including the bottom itself. While the top area of the surface of the one or more gaps may be may be defined as the top 90%, 75%, 50%, or even 25% of the total height of the gap.

In a second step 120 a second reactant may be provided to the surface; and in a third step 130 the first reactant may cause initiation of the reaction of the second reactant in the bottom area of the surface in a stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactants leaving a top area of the surface of the one or more gaps which was not provided with the first reactant initially substantially empty.

The first reactant may comprise a Lewis acid metal or metalloid. The Lewis acid metal or metalloid is selected from the group consisting of aluminum, boron, magnesium, scandium, lanthanum, yttrium, zirconium or hafnium. The first reactant may be trimethylaluminium (TMA), for example.

The second reactant may comprise silanol vapor to form a silica layer in reaction with the TMA as described in the article “Rapid Vapor Deposition of Highly Conformal Silica Nanolaminates” by Dennis Hausmann et al. Science Vol. 298, 11 Oct. 2002, page 402 to 405 incorporated herein by reference. The second reactant may be tris(tert-pentoxy)silanol or tris(tert-butoxy)silanol. TMA and silanol may rapidly react into a silica layer greater than 2 nm, for example 10 nm, per cycle.

Excess reactant and byproduct may be removed after providing a first, and or second reactant to prevent reactions occurring elsewhere. The deposition method may be repeated multiple cycles to fill the gap from the bottom area to the top area such that the refilling material will not form a constriction near the top of the gap before it is completely filled.

The second reactant may be introduced with a relatively large dose compared to the dose in which the first reactant may be provided to accommodate the stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactant.

FIG. 3 depicts a method for step 110 in FIG. 1 which is providing the bottom area of the surface of the one or more gaps with the first reactant. Step 110 may comprise the step 101 to provide the first reactant to the top and the bottom area of the surface.

The first reactant may comprise a Lewis acid metal or metalloid. The Lewis acid metal or metalloid is selected from the group consisting of aluminum, boron, magnesium, scandium, lanthanum, yttrium, zirconium or hafnium. The first reactant may be trimethylaluminium (TMA), for example. The TMA may be binding with the OH present in the top and bottom area of the surface of the gaps in step 101.

Subsequently in step 102 the first reactant may be passivated in the top area. Passivating the first reactant in the top area of the one or more gaps may be done by providing a plasma to passivate the first reactant in the top area while the first reactant remains active in the bottom area because the plasma gets weaker going down in the small trench. The plasma may be a nitrogen plasma passivating the TMA in the top area while active TMA remains in the bottom area. It is believed that the plasma may be nitridating the adsorbed TMA in the top area making it unreactive for the subsequent reaction steps

The process cycle with a plasma may be performed using a semiconductor processing apparatus comprising:

one or more reaction chambers for accommodating a substrate provided with gaps created during manufacturing of a feature on the substrate;

a first source for a first reactant in gas communication via a first valve with one of the reaction chambers; and,

a second source for a second reactant in gas communication via a second valve with one of the reaction chambers; wherein the apparatus comprises:

a plasma gas source for a plasma gas in gas communication via a plasma gas valve with one of the reaction chambers;

a radio frequency power source constructed and arranged to create a plasma of the plasma gas;

a heater constructed and arranged to heat the substrate in one of the reaction chambers and,

a controller operably connected to the first, second and plasma gas valves, the radio frequency power source and the heater and configured and programmed to control:

a timing and an amount of the first, the plasma gas, and the radio frequency source to use the first source, the plasma gas source and the radiofrequency power source to provide the first reactant substantially in a bottom area of the surface of the gap; and,

a timing and an amount of the second reactant and the heater to deposit at an alleviated temperature in a stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactants causing a reaction in the gap leaving a top area of the surface of the one or more gaps which was not provided with the first reactant initially substantially empty.

Such an apparatus may be illustrated in FIG. 1A, for example. FIG. 1A is a schematic view of a PEALD apparatus, desirably in conjunction with controls programmed to conduct the sequences described herein, usable in some embodiments of the present invention. In this figure, by providing a pair of electrically conductive flat-plate electrodes 4, 2 in parallel and facing each other in the interior 11 (reaction zone) of a reaction chamber 3, applying HRF power (13.56 MHz or 27 MHz) 20 to one side, and electrically grounding the other side 12, a plasma is excited between the electrodes. A temperature regulator is provided in a lower stage 2 (the lower electrode), and a temperature of a substrate 1 placed thereon is kept constant at a given temperature. The upper electrode 4 serves as a shower plate as well, and reactant gas (and noble gas) and precursor gas are introduced into the reaction chamber 3 through a gas line 21 and a gas line 22, respectively, and through the shower plate 4.

Additionally, in the reaction chamber 3, a circular duct 13 with an exhaust line 7 is provided, through which gas in the interior 11 of the reaction chamber 3 is exhausted. Additionally, a transfer chamber 5 disposed below the reaction chamber 3 is provided with a seal gas line 24 to introduce seal gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5 wherein a separation plate 14 for separating the reaction zone and the transfer zone is provided (a gate valve through which a wafer is transferred into or from the transfer chamber 5 is omitted from this figure). The transfer chamber is also provided with an exhaust line 6. In some embodiments, the deposition of multi-element film and surface treatment are performed in the same reaction space, so that all the steps can continuously be conducted without exposing the substrate to air or other oxygen-containing atmosphere. In some embodiments, a remote plasma unit can be used for exciting a gas.

In some embodiments, in the apparatus depicted in FIG. 1A, the system of switching flow of an inactive gas and flow of a precursor gas illustrated in FIG. 1B (described earlier) can be used to introduce the precursor gas in pulses without substantially fluctuating pressure of the reaction chamber.

In some embodiments, a dual chamber reactor (two sections or compartments for processing wafers disposed closely to each other) can be used, wherein a reactant gas and a noble gas can be supplied through a shared line whereas a precursor gas is supplied through unshared lines.

The apparatus may be provided with a heater to activate the reactions by elevating the temperature of one or more of the substrate, the first, second and third reactants. Exemplary single wafer reactors, designed specifically to perform ALD processes, are commercially available from ASM International NV (Almere, The Netherlands) under the tradenames Pulsar®, Emerald®, Dragon® and Eagle®. Exemplary batch ALD reactors, designed specifically to perform ALD processes, are commercially also available from and ASM International N.V under the tradenames A400™ and A412™.

The apparatus may be provided with a radiofrequency source operably connected with the controller constructed and arranged to produce a plasma of the first, second or third reactant. The plasma enhanced atomic layer deposition PEALD may be performed in an Eagle® XP8 PEALD reactor available from ASM International N.V. of Almere, the Netherlands which apparatus comprises a plasma source to activate one or more of the reactants.

A skilled artisan will appreciate that the apparatus includes one or more controller(s) (not shown) programmed or otherwise configured to cause the deposition and reactor cleaning processes described elsewhere herein to be conducted. The controller(s) are communicated with the various power sources, heating systems, pumps, robotics, and gas flow controllers or valves of the reactor, as will be appreciated by the skilled artisan.

FIG. 4 depicts an alternative method for step 110 in FIG. 2 providing the bottom area of the surface of the one or more gaps with the first reactant. In step 103 reactive sites present in the top area of the surface may be passivated. Subsequently, step 104 may comprise providing the first reactant to the top and the bottom area of the surface to react with the remaining active sites on the bottom surface.

The first reactant may comprise a Lewis acid metal or metalloid. The Lewis acid metal or metalloid is selected from the group consisting of aluminum, boron, magnesium, scandium, lanthanum, yttrium, zirconium or hafnium. The first reactant may be trimethylaluminium (TMA), for example.

Passivating reactive sites of the top area of the surface in step 103 may comprise providing a plasma to passivate the active sites present in the top area while the active sites in the bottom area may be remaining because of the plasma and thereby the effect of the plasma gets weaker going down in the small trench. The plasma may be a nitrogen or argon plasma. The TMA may react with the active sites in the bottom area while it will not react in the passivated top area leaving only TMA in the bottom area. More specifically the TMA may be binding with the OH groups in the bottom area of the surface of the gaps in step 104. The same apparatus as mentioned in relation to FIG. 3 may be used for this method.

FIG. 5 depicts a further alternative method for step 110 in FIG. 2 providing the bottom area of the surface of the one or more gaps with the first reactant. The further alternative method comprising:

providing a polymer material in the bottom area of the surface in step 105;

infiltrating the polymer material with the first reactant in step 106; and

removing the polymer material from the bottom area while allowing the first reactant to remain in step 107.

The polymer material in the bottom area of the surface may be provided by providing a polymer material in the top and bottom area in step 105. The polymer material may polyimide or polyamic acid polymer or a directed self-assembly polymer. Thereafter a plasma may be provided to remove the polymer material from the top area while the polymer in the bottom area may be remaining because the plasma and thereby the etching effect of the plasma gets weaker going down in the small trench. The plasma may be a nitrogen, oxygen, hydrogen, fluorine or argon plasma or any combination of them.

The polymer material may be infiltrated with the first reactant in step 106. The first reactant may comprise a Lewis acid metal or metalloid. The Lewis acid metal or metalloid is selected from the group consisting of aluminum, boron, magnesium, scandium, lanthanum, yttrium, zirconium or hafnium. The first reactant may be trimethylaluminium (TMA), for example.

In step 107 the polymer material may be removed from the bottom area while allowing the first reactant to remain by annealing the material in an oxygen containing atmosphere. This annealing may, for example, be done in 15 min at 550° C. in air. The polymer material may be, for example, a polyimide or polyamic acid polymer or a directed self-assembly polymer.

Below table shows six examples of:

providing a polymer material polyimide (PI) in a film on a surface;

infiltrating the polymer material with the first reactant TMA; and

removing the polymer material while allowing the first reactant to remain by annealing in an oxygen environment.

Thickness (nm) Deposition As After 15 min at % thickness Temp. ° C. Film deposited 550° C. in air remaining 160 10x(12PI + 29.6 3.9 13.18% TMA) 160 PI + TMA 17.2 1.9 11.05% 160 PI 32.2 0.4 1.24% 130 10x(12PI + 31.6 6.9 21.84% TMA) 130 PI + TMA 29.9 1.9 6.35% 130 PI 28.7 0 0.00%

The fourth and fifth column of the examples with TMA show that a thickness of TMA is remaining on the surface after 15 min at 550° C. in air. The examples without TMA show that the PI can be removed almost completely by annealing in air. The same apparatus as mentioned in relation to FIG. 3 may be used for this method.

After the methods of FIGS. 3 to 5 a layer of TMA is remaining in the bottom area. The method may further comprise in step 120 of FIG. 1 heating the substrate (e.g. between 100 and 300° Celsius) and providing the second reactant comprising silanol vapor to form a silica layer in reaction with the TMA.

The silanol of step 120 may be tris(tert-pentoxy)silanol or tris(tert-butoxy)silanol. TMA and silanol may rapidly react into a layer greater than 2 nm, for example 10 nm, per cycle.

The silanol vapor may be introduced in an amount sufficient to saturate the surface of the one or more gaps. The silanol vapour may react with the Lewis acid metal or metalloid. The Lewis acid metal or metalloid may react as a catalyst catalyzing the reaction between silanol molecules and the growing siloxane chains.

It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases.

The subject matter of the present disclosure includes all novel and nonobvious combinations and sub-combinations of the various processes, systems, and configurations, and other features, functions, acts, and/or properties disclosed herein, as well as any and all equivalents thereof. 

The invention claimed is:
 1. A method for filling one or more gaps created during manufacturing of a feature on a substrate by a deposition method comprising: providing a bottom area of a surface of the one or more gaps with a first reactant; providing a second reactant to the substrate; allowing, in a film deposition cycle, the first reactant to initiate reaction of the second reactant in the bottom area of the surface in a stoichiometric ratio of one molecule of the first reactant to multiple molecules of the second reactant, to form a layer of deposited material in the bottom area, leaving a top area of the surface of the one or more gaps which was not provided with the first reactant initially substantially empty; and repeating the cycle, such that the deposited material forms layer-by-layer in the one or more gaps from the bottom area upwards, wherein providing the bottom area of the surface of the one or more gaps with the first reactant comprises: providing a polymer material in the bottom area of the surface; infiltrating the polymer material with the first reactant; and removing the polymer material from the bottom area while allowing the first reactant to remain in the bottom area.
 2. The method according to claim 1, wherein the method comprises removing excess reactant and byproduct after providing a first, and or second reactant.
 3. The method according to claim 1, wherein the deposition method is repeated multiple times to fill the gap from the bottom area to the top area.
 4. The method according to claim 1, wherein the second reactant is introduced with a relatively large dose compared to the dose in which the first reactant is provided.
 5. The method according to claim 1, wherein providing the bottom area of the surface of the one or more gaps with the first reactant comprises: providing the first reactant to the top and the bottom area of the surface of the one or more gaps; and, using a plasma, passivating the first reactant in the top area of the one or more gaps to render the first reactant less active in the top area relative to the bottom area.
 6. The method according to claim 5, wherein the first reactant comprises one or more of a Lewis acid and a metalloid.
 7. The method according to claim 6, wherein the plasma comprises a nitrogen plasma.
 8. The method according to claim 1, wherein providing the bottom area of the surface of the one or more gaps with the first reactant comprises: passivating reactive sites on the top area of the surface; and, providing the first reactant to the top and the bottom area of the surface to react with the remaining active sites on the bottom surface, wherein the first reactant does not react with the passivated sites.
 9. The method according to claim 8, wherein passivating reactive sites of the top area of the surface comprises providing a plasma to passivate the active sites from the top area.
 10. The method according to claim 9, wherein the plasma is a nitrogen and/or argon plasma.
 11. The method according to claim 1, wherein providing a polymer material in the bottom area of the surface comprises providing a polymer material in the top and bottom area and providing a plasma to remove the polymer material from the top area.
 12. The method according to claim 11, wherein the plasma comprises nitrogen, oxygen, hydrogen, fluorine and/or argon.
 13. The method according to claim 1, wherein removing the polymer material from the bottom area while allowing the first reactant to remain comprises annealing the material in an oxygen comprising atmosphere.
 14. The method according to claim 1, wherein the polymer material comprises a polyimide or a polyamic acid polymer or a directed self-assembly polymer.
 15. The method according to claim 1, wherein the first reactant comprises a Lewis acid metal or metalloid.
 16. The method according to claim 15, wherein the Lewis acid metal or metalloid is selected from the group consisting of aluminium, boron, magnesium, scandium, lanthanum, yttrium, zirconium or hafnium.
 17. The method according to claim 16, wherein the first reactant comprises trimethylaluminium (TMA).
 18. The method according to claim 1, wherein the method comprises heating the substrate and the second reactant comprises silanol vapor to form a silica layer.
 19. The method according to claim 18, wherein the silanol comprises tris(tert-pentoxy)silanol or tris(tert-butoxy)silanol. 